CN104107711A - Fluidized bed catalyst for preparing propylene from methanol and preparation method of fluidized bed catalyst - Google Patents
Fluidized bed catalyst for preparing propylene from methanol and preparation method of fluidized bed catalyst Download PDFInfo
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Abstract
The invention discloses a fluidized bed catalyst for preparing propylene from methanol and a preparation method of the fluidized bed catalyst. The preparation method comprises the steps of firstly carrying out effective dispersion and ball-spraying forming on ZSM-5 molecular sieve raw powder by virtue of a dispersing agent, and then modifying the formed catalyst by virtue of one or more salt solutions in nonmetal and rare earth metals through a dipping method, so as to obtain the fluidized bed catalyst. The fluidized bed catalyst has the beneficial effects that the dispersing agent is low in cost and is easily available, and the preparation method of the catalyst is simple; the fluidized bed catalyst is applied to a fluidized bed reaction for preparing propylene from methanol, when the reaction temperature is 500 DEG C and the weight hourly space velocity of methanol is 4h<-1>, the conversion rate of methanol is more than 99%, and the selectivity of propylene is more than 46%.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of fluid catalyst and preparation method thereof, especially a kind of preparing propylene from methanol fluid catalyst and preparation method thereof.
Background technology
Propylene is one of important organic chemical industry's basic material being only second to by ethene, mainly for the production of organic matters such as polypropylene, acrylonitrile, acrylic acid, expoxy propane, isopropyl alcohol, glycerine and cumenes.Recent two decades comes, and the application of propylene constantly expands, and replaces the extensive use of the synthetic resin of the nonplastic materials such as paper, steel, timber and costliness by propylene downstream product, makes the growth rate of World Propylene demand faster than ethene.
Propylene is mainly obtained through steam cracking or catalytic cracking by petroleum at present, and 57% propylene is produced by steam cracking device, and 35% propylene is from the catalytic cracking unit accessory substance of oil plant.Along with the continuous decrease of petroleum resources reserves, oil price constantly increases, and makes the cost of material of production of propylene continue to rise, and therefore each state is all improving original petroleum path technique in the world, the Non oil-based route of active research exploitation is simultaneously produced propylene technology, to reduce production of propylene cost.Non oil-based route technology mainly utilizes coal, natural gas or living beings through methyl alcohol or dimethyl ether synthesizing propylene again.Current domestic coal methyl alcohol production capacity processed is seriously superfluous, methanol device utilization of capacity less than 50%, and therefore exploitation has high added value preparing propylene from methanol (MTP) technique and can be superfluous methyl alcohol production capacity good outlet is provided.
MTP reaction is a kind of gas-solid heterogeneous catalytic reaction, conventionally adopt acid molecular sieve catalyst, the eighties in 20th century, U.S. Mobil company was in the time of research preparing gasoline by methanol Catalytic processes, finding by the change of process conditions, can be low-carbon alkene by methanol conversion taking the ZSM-5 molecular sieve after modifying as catalyst.Take the lead in having carried out with the ZSM-5 molecular sieve research of preparing propylene by methanol transformation industrialization technology of LURGI of Germany, they adopt fixed bed reactors taking high-silicon small grain ZSM-5 molecular sieve as catalyst, prepare ZSM-5 catalyst series by Cd and Zn modification, propylene one way is selectively 35～40% left and right, heavy component circulation Returning reactor, can make propene yield reach 71.2% (patent No.: CN103263944A).By fluid bed preparing propylene from methanol (FMTP) technique of China National Chemical Engineering Group Corporation, Tsing-Hua University, three unit consolidation exploitations of Anhui Huai Hua group, employing has the SAPO-18/34 molecular sieve of multi-level nano-structure and hands over phase mixed crystal catalyst, the multistage fluidized bed reactor of subregion fluidisation control back-mixing, reaction in two steps, the first step is carried out MTO reaction in methanol-to-olefins main reaction region, product, through gas separation system, is isolated C
2and C
2following component, C
4and C
4above component is returned to fluidized bed reaction, carries out EBTP reaction in olefin reaction district, and reacting gas enters piece-rate system and separates (patent No.: CN100551883C); First step MTO reacts propene yield approximately 38.2%, and P/E is than approximately 1.18, and after second step EBTP reaction, propene yield can reach 67.3%.
Preparing propylene from methanol reaction belongs to the exothermic reaction of hydrocarbon, the about 23.1KJ/mol of ethene heat release of 1 mole of the every generation of methyl alcohol in the time of 427 DEG C, and the propylene heat release 92.9KJ/mol that every generation is 1 mole, and the butylene heat release of 1 mole of every generation reaches 150.0KJ/mol.So many heat cannot be disperseed timely and effectively and the inner hot-spot of the device that easily induces reaction and cause a large amount of side reactions to occur in fixed bed reactors; Also exist catalyst frequently to switch regeneration, the problem (patent No.: CN101417235) of complicated operation simultaneously.And existing FMTP technology is subject to the restriction of the architectural features such as the aperture of catalyst own, first step MTO reaction propene yield and P/E are high than not, and in first step reaction, approximately have 32.4% ethene need to separate freshening, have greatly increased the energy consumption of installing.
Sieve with respect to SAPO Series Molecules, ZSM-5 molecular sieve has larger orifice diameter, is conducive to formation and the diffusion of propylene, therefore the ZSM-5 molecular sieve catalyst after modification modulation aperture and acidity is used for fluidized-bed reaction by the present invention, both can effectively solve the frequent regeneration phenomenon that fixed bed moves heat difficulty, catalyst, can avoid again SAPO catalyst series because the propylene once through yield that the nature and characteristics such as structure cause is low, P/E is than low, the problems such as a large amount of ethene freshening energy consumption height.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparing propylene from methanol fluid catalyst and preparation method thereof is provided, first this catalyst adopts dispersant effectively to disperse the former powder of ZSM-5 molecular sieve and sprays ball forming, then use one or more salting liquids in nonmetal, rare earth metal, the catalyst of method by dipping after to moulding carries out modification and obtains fluid catalyst, and its raw material is cheap and easy to get, method for preparing catalyst is simple.
The object of the invention is to be achieved through the following technical solutions:
This preparing propylene from methanol fluid catalyst, in quality percentage composition, comprises following component:
10～70% ZSM-5 molecular sieve, 20～60% dispersant, 10～35% binding agent, the pore creating material of 0-5%, 0～5% P
2o
5, 0～5% La
2o
3.
Further, above-mentioned ZSM-5 is Hydrogen ZSM-5 molecular sieve; SiO
2/ Al
2o
3mol ratio is 25～300, and crystal grain is 20～5000nm.
Further, above-mentioned dispersant is selected from a kind of or its several mixing in kaolin, imvite, boehmite, pure silicon powder etc.
Further, binding agent is selected from a kind of or its several mixing in Ludox, aluminium colloidal sol, aluminum phosphate.
Further, above-mentioned pore creating material is selected from a kind of or its several mixing in graphite powder, starch, sesbania powder.
Further, above P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, phosphoric acid dihydro amine or phosphoric acid.La
2o
3precursor be selected from the salt of solubility, preferably lanthanum nitrate hexahydrate.
A preparation method for above-mentioned preparing propylene from methanol fluid catalyst, specifically carries out according to following steps:
A) proportionally ZSM-5 molecular sieve is mixed with dispersant, binding agent and pore creating material, after spray shaping, dry, roasting, obtain molecular sieve catalyst precursor;
B) catalyst precursor step a) being obtained floods in the aqueous solution of soluble sources, and drying, roasting obtain phosphorus modified catalyst;
C) phosphorus modified catalyst step b) being obtained floods in the aqueous solution in required lanthanum source, and drying, roasting obtain preparing propylene from methanol fluid catalyst.
Further, described step b) and c) in the temperature of dipping be room temperature～90 DEG C, the time of dipping is 1～48 hour.Above-mentioned steps a), b) and c) middle baking temperature is 100～250 DEG C, and be 1～24 hour drying time.Step a), b) and c) middle sintering temperature is 350～650 DEG C, and roasting time is 3～24 hours.
The present invention has following beneficial effect:
In preparing propylene from methanol fluid catalyst of the present invention and preparation method thereof, the strong acidic site of Hydrogen ZSM-5 is preparing propylene from methanol main reaction active sites, adding of dispersant, can effectively disperse strong acidic site on catalyst, increase the touch opportunity of material benzenemethanol and strong acid active sites; Can enter into the intracrystalline duct of molecular sieve through the oxide of dipping, cause on the one hand surface, duct dealuminzation, occur duct defect, make aperture become large, increase the diffusion rate of product, reduce the generation of side reaction; Can form a kind of new hydroxyl on surface, duct adding of modifier on the other hand, have new acidic site to produce, reaction is played to facilitation.Thereby amount and the combination of dispersant and modifier in control catalyst, can reach the object of preparing propylene from methanol distribution of reaction products being carried out to Effective Regulation.The dispersant that the present invention relates to is cheap and easy to get, method for preparing catalyst is simple; For preparing propylene from methanol fluidized-bed reaction, when 500 DEG C of reaction temperatures, the mass space velocity of methyl alcohol is 4h
-1condition under, methanol conversion is greater than 99%, Propylene Selectivity is greater than 46%.
Detailed description of the invention
First the present invention relates to a kind of preparing propylene from methanol fluid catalyst, and this catalyst is in quality percentage composition, and the component comprising has: 10～70% ZSM-5 molecular sieve, 20～60% dispersant, 10～35% binding agent, the pore creating material of 0-5%, 0～5% P
2o
5, 0～5% La
2o
3.Wherein P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, phosphoric acid dihydro amine or phosphoric acid.La
2o
3precursor be selected from the salt of solubility, preferably lanthanum nitrate hexahydrate.ZSM-5 is Hydrogen ZSM-5 molecular sieve; SiO
2/ Al
2o
3mol ratio is 25～300, and crystal grain is 20～5000nm.Dispersant is selected from a kind of or its several mixing in kaolin, imvite, boehmite, pure silicon powder etc.Binding agent is selected from a kind of or its several mixing in Ludox, aluminium colloidal sol, aluminum phosphate.Pore creating material is selected from a kind of or its several mixing in graphite powder, starch, sesbania powder.
The invention still further relates to the preparation method of above-mentioned preparing propylene from methanol fluid catalyst, specifically carry out according to following steps:
A) proportionally ZSM-5 molecular sieve is mixed with dispersant, binding agent and pore creating material, after spray shaping, dry, roasting, obtain molecular sieve catalyst precursor;
B) catalyst precursor step a) being obtained floods in the aqueous solution of soluble sources, and drying, roasting obtain phosphorus modified catalyst;
C) phosphorus modified catalyst step b) being obtained floods in the aqueous solution in required lanthanum source, and drying, roasting obtain preparing propylene from methanol fluid catalyst.
Catalyst of the present invention is evaluated by fluid bed microreactor, and taking methyl alcohol as raw material, water is diluent, and reaction temperature is 500 DEG C, and reaction pressure is normal pressure, and the mass ratio of methanol/water is 2:1, and air speed is 4h
-1, the conversion ratio of material benzenemethanol is greater than 99%, and Propylene Selectivity is greater than 46%.Obtain good technique effect.
Below by comparative example and embodiment comparison the present invention is further elaborated.
Comparative example 1:
Take 600g silica alumina ratio SiO
2/al
2o
3be 25, the molecular sieve that particle diameter is 2000nm, with 200g Ludox, 300g pure silicon powder and a certain amount of water mix, and spray shaping makes the microballoon that fluidized-bed reactor is used, and drying, 400 DEG C of roastings obtain molecular sieve catalyst in 20 hours, are numbered KB-01.
Comparative example 2:
Take 500g silica alumina ratio SiO
2/al
2o
3be 107, the molecular sieve that particle diameter is 100nm, with 400g aluminium colloidal sol, 800g boehmite, 20g sesbania powder and a certain amount of water mix, and spray shaping makes the microballoon that fluidized-bed reactor is used, drying, 600 DEG C of roastings obtain molecular sieve catalyst in 5 hours, are numbered KB-02.
Comparative example 3:
Take 1000g silica alumina ratio SiO
2/al
2o
3be 262, particle diameter is the molecular sieve of 5000nm, with 300g aluminum phosphate, kaolin, 70g starch and a certain amount of water of 400g imvite, 200g mix, spray shaping, make the microballoon that fluidized-bed reactor is used, drying, 500 DEG C of roastings obtain molecular sieve catalyst in 10 hours, are numbered KB-03.
Comparative example 1～3rd, without reactivity worth nonmetal, rare-earth metal modified catalyst, is mainly in order to compare with the reactivity worth of modification rear catalyst.
Embodiment 1:
Take 500g silica alumina ratio SiO
2/al
2o
3be 25, the molecular sieve that particle diameter is 2000nm, with 200g Ludox, 300g pure silicon powder and a certain amount of water mix, and spray shaping makes the microballoon that fluidized-bed reactor is used, and drying, 500 DEG C of roastings obtain molecular sieve precursor for 3 hours; 60 DEG C of dippings modification 24 hours in the aqueous solution that 200g molecular sieve precursor is made at 12g diammonium hydrogen phosphate, 180 DEG C of dry 600 DEG C of roastings 6 hours again after 15 hours, obtain molecular sieve catalyst, are numbered LC-01.
Embodiment 2:
Take 500g silica alumina ratio SiO
2/al
2o
3be 60, the molecular sieve that particle diameter is 500nm, with 200g Ludox, 100g pure silicon powder, 15g sesbania powder and a certain amount of water mix, and spray shaping makes the microballoon that fluidized-bed reactor is used, and drying, 550 DEG C of roastings obtain molecular sieve precursor for 8 hours; In the aqueous solution that 200g molecular sieve precursor is made at 25g phosphoric acid, under room temperature, flood modification 24 hours, 180 DEG C of dry 450 DEG C of roastings 24 hours again after 15 hours, obtain molecular sieve catalyst, are numbered LC-02.
Embodiment 3:
Take 500g silica alumina ratio SiO
2/al
2o
3be 107, the molecular sieve that particle diameter is 20nm, with 400g Ludox, 700g imvite, 24g graphite powder and a certain amount of water mix, and spray shaping makes the microballoon that fluidized-bed reactor is used, and drying, 450 DEG C of roastings obtain molecular sieve precursor for 24 hours; 80 DEG C of dippings modification 4 hours in the aqueous solution that 200g molecular sieve precursor is made at 15g ammonium dihydrogen phosphate (ADP), 120 DEG C of dry 500 DEG C of roastings after 10 hours again after 8 hours, 90 DEG C of dippings modification 5 hours in the aqueous solution being made at 2.5g lanthanum nitrate hexahydrate again, 120 DEG C are dried 8 hours, 500 DEG C of roastings obtain catalyst in 18 hours, are numbered LC-03.
Embodiment 4:
Take 500g silica alumina ratio SiO
2/al
2o
3be 174, particle diameter is 1500nm molecular sieve, mixes spray shaping with 400g Ludox, 100g kaolin, 400g boehmite, 60g starch and a certain amount of water, make the microballoon that fluidized-bed reactor is used, drying, 550 DEG C of roastings obtain molecular sieve precursor for 24 hours; In the aqueous solution that 200g molecular sieve precursor is made at 10g diammonium hydrogen phosphate, under room temperature, flood modification 48 hours, 120 DEG C of 500 DEG C of roastings after 10 hours again in dry 8 hours, in the aqueous solution being made at 14g lanthanum nitrate hexahydrate again, 60 DEG C flood 36 hours, 120 DEG C are dried 8 hours, 650 DEG C of roastings obtain catalyst in 5 hours, are numbered LC-04.
Embodiment 5:
Take 500g silica alumina ratio SiO
2/al
2o
3be 300, particle diameter is 2500nm molecular sieve, mixes spray shaping with 300g Ludox, 100g pure silicon powder, 500g boehmite, 20g sesbania powder and a certain amount of water, make the microballoon that fluidized-bed reactor is used, drying, 450 DEG C of roastings obtain molecular sieve precursor for 24 hours; In the aqueous solution that 200g molecular sieve precursor is made at 10g diammonium hydrogen phosphate, 80 DEG C flood 12 hours, 120 DEG C are dried 8 hours, 550 DEG C of roastings are after 10 hours, 70 DEG C of dippings modification 16 hours in the aqueous solution being made at 23g lanthanum nitrate hexahydrate again, 120 DEG C are dried 8 hours, 550 DEG C of roastings obtain catalyst in 10 hours, are numbered LC-05.
Embodiment 6:
Reaction is carried out in miniature fluidized bed reaction, and reaction condition is as follows: loaded catalyst 10g, and 500 DEG C of reaction temperatures, 650 DEG C of regeneration temperatures, reaction pressure is normal pressure, with micro-feed pump charging.The mass ratio of methanol/water is 2:1, and air speed is 4h
-1, product gas samples online through Agilent7890A chromatogram, sample analysis when reaction 60min, and methanol conversion and product distribute in table 1.
Table 1MTP fluidized-bed reaction methanol conversion and product distribute
Note: in table 1, the component of product distribution less than 100% is CO, CO
2and C
2h
6, due to selectively very low, in form, do not list.
In order to further illustrate the present invention, provide several further embodiments of the present invention below:
Embodiment 7:
The preparing propylene from methanol fluid catalyst of the present embodiment, in quality percentage composition, comprises following component: 10% ZSM-5 molecular sieve, wherein SiO
2/ Al
2o
3mol ratio is 300, and particle diameter is 2500nm; 60% dispersant boehmite; 25% binding agent aluminium colloidal sol; 2% pore creating material sesbania powder, precursor is selected from 3% P of diammonium hydrogen phosphate
2o
5.
Embodiment 8
The preparing propylene from methanol fluid catalyst of the present embodiment, in quality percentage composition, comprises following component: 25% ZSM-5 molecular sieve, wherein silica alumina ratio SiO
2// Al
2o
3be 255, particle diameter is 1500nm; 32% dispersant kaolin, 35% binding agent aluminum phosphate, 5% pore creating material starch, precursor is selected from 3% La of lanthanum nitrate hexahydrate
2o
3.
Embodiment 9
The preparing propylene from methanol fluid catalyst of the present embodiment, in quality percentage composition, comprises following component: 45% ZSM-5 molecular sieve, wherein silica alumina ratio SiO
2/
/al
2o
3be 194, particle diameter is 1500nm; 25% dispersant pure silicon powder, 20% adhesive silicon sol, 4% pore creating material graphite powder, precursor is selected from 4% P of phosphoric acid
2o
5, precursor is selected from 2% La of lanthanum nitrate hexahydrate
2o
3.
Embodiment 10
The preparing propylene from methanol fluid catalyst of the present embodiment, in quality percentage composition, comprises following component: 58% ZSM-5 molecular sieve, wherein silica alumina ratio SiO
2// Al
2o
3be 107, particle diameter is 200nm; 20% dispersant boehmite, 15% binding agent aluminium colloidal sol, does not add pore creating material, and precursor is selected from 2% P of phosphoric acid
2o
5, and 5% La of lanthanum nitrate hexahydrate
2o
3.
Embodiment 11
The preparing propylene from methanol fluid catalyst of the present embodiment, in quality percentage composition, comprises following component: 70% ZSM-5 molecular sieve, wherein silica alumina ratio SiO
2/al
2o
3be 25, particle diameter is 800nm; 20% dispersant boehmite; 10% binding agent aluminium colloidal sol, does not add pore creating material; Mix with a certain amount of water, spray shaping, makes the microballoon that fluidized-bed reactor is used, and drying, roasting obtain test catalyst.
The temperature of above 7～11 embodiment dipping is room temperature～90 DEG C, and the time of dipping is 1～48 hour; Baking temperature is 100～250 DEG C, and be 1～24 hour drying time; Sintering temperature is 350～650 DEG C, and roasting time is 3～24 hours.
Embodiment 12
Preparing propylene from methanol fluid catalyst in the present embodiment, in quality percentage composition, comprises 30% ZSM-5 molecular sieve, 40% dispersant, 20% binding agent, 5% P
2o
5, 5% La
2o
3.Described ZSM-5 is Hydrogen ZSM-5 molecular sieve, SiO
2/ Al
2o
3mol ratio is 25～300, and crystal grain is 20～5000nm.Described dispersant is selected from a kind of or its several mixing in kaolin, imvite, boehmite, pure silicon powder etc.; Binding agent is selected from a kind of or its several mixing in Ludox, aluminium colloidal sol, aluminum phosphate.Described pore creating material is selected from a kind of or its several mixing in graphite powder, starch, sesbania powder.P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, phosphoric acid dihydro amine or phosphoric acid.La
2o
3precursor be selected from the salt of solubility, preferably lanthanum nitrate hexahydrate.Carry out according to following steps:
A) proportionally ZSM-5 molecular sieve is mixed with dispersant, binding agent and pore creating material, after spray shaping, dry, roasting, obtain molecular sieve catalyst precursor;
B) catalyst precursor step a) being obtained floods in the aqueous solution of soluble sources, and drying, roasting obtain phosphorus modified catalyst;
C) phosphorus modified catalyst step b) being obtained floods in the aqueous solution in required lanthanum source, and drying, roasting obtain preparing propylene from methanol fluid catalyst.
Above step b) and c) in the temperature of dipping be room temperature～90 DEG C, the time of dipping is 1～48 hour.Step a), b) and c) middle baking temperature is 100～250 DEG C, and be 1～24 hour drying time.Step a), b) and c) middle sintering temperature is 350～650 DEG C, and roasting time is 3～24 hours.
Claims (10)
1. a preparing propylene from methanol fluid catalyst, is characterized in that, in quality percentage composition, comprises following component:
10～70% ZSM-5 molecular sieve, 20～60% dispersant, 10～35% binding agent, the pore creating material of 0-5%, 0～5% P
2o
5, 0～5% La
2o
3.
2. preparing propylene from methanol fluid catalyst according to claim 1, is characterized in that, described ZSM-5 is Hydrogen ZSM-5 molecular sieve, SiO
2/ Al
2o
3mol ratio is 25～300, and crystal grain is 20～5000nm.
3. preparing propylene from methanol fluid catalyst according to claim 1, is characterized in that, described dispersant is selected from a kind of or its several mixing in kaolin, imvite, boehmite, pure silicon powder etc.; Binding agent is selected from a kind of or its several mixing in Ludox, aluminium colloidal sol, aluminum phosphate.
4. preparing propylene from methanol fluid catalyst according to claim 1, is characterized in that, described pore creating material is selected from a kind of or its several mixing in graphite powder, starch, sesbania powder.
5. preparing propylene from methanol fluid catalyst according to claim 1, is characterized in that P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, phosphoric acid dihydro amine or phosphoric acid.
6. preparing propylene from methanol fluid catalyst according to claim 1, is characterized in that La
2o
3precursor be selected from the salt of solubility, preferably lanthanum nitrate hexahydrate.
7. a preparation method for preparing propylene from methanol fluid catalyst described in claim 1-6 any one, is characterized in that, carries out according to following steps:
A) proportionally ZSM-5 molecular sieve is mixed with dispersant, binding agent and pore creating material, after spray shaping, dry, roasting, obtain molecular sieve catalyst precursor;
B) catalyst precursor step a) being obtained floods in the aqueous solution of soluble sources, and drying, roasting obtain phosphorus modified catalyst;
C) phosphorus modified catalyst step b) being obtained floods in the aqueous solution in required lanthanum source, and drying, roasting obtain preparing propylene from methanol fluid catalyst.
8. preparing propylene from methanol fluid catalyst and preparation method thereof according to claim 7, is characterized in that, described step b) and c) temperature of dipping be room temperature～90 DEG C, the time of dipping is 1～48 hour.
9. preparing propylene from methanol fluid catalyst and preparation method thereof according to claim 7, is characterized in that, described step a), b) and c) in baking temperature be 100～250 DEG C, be 1～24 hour drying time.
10. preparing propylene from methanol fluid catalyst and preparation method thereof according to claim 7, is characterized in that, described step a), b) and c) in sintering temperature be 350～650 DEG C, roasting time is 3～24 hours.
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| CN108262069A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The preparation method of fluid catalyst, the catalyst prepared and its purposes |
| CN108262069B (en) * | 2017-01-04 | 2021-06-22 | 中国石油化工股份有限公司 | Method for producing a fluidized bed catalyst, catalyst produced and use thereof |
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